JP2021098372A - Thermal transfer sheet, intermediate transfer medium, printed matter produced using the thermal transfer sheet or the intermediate transfer medium, method for manufacturing printed matter and system for manufacturing printed matter - Google Patents

Abstract

To provide a thermal transfer sheet having high antibacterial property and foil holding property.SOLUTION: A thermal transfer sheet includes a first base material and a transfer layer including at least a peeling layer. The peeling layer contains a resin material and antibacterial particles. An average particle diameter of the antibacterial particles is 1 μm or more and 8 μm or less. In the peeling layer, a content of the antibacterial particles with respect to 100 pts.mass of the resin material is 2.8 pts.mass or more and 8 pts.mass or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a thermal transfer sheet, an intermediate transfer medium, a printed matter manufactured using the thermal transfer sheet or the intermediate transfer medium, a method for producing a printed matter, and a printed matter manufacturing system.

A thermal transfer image is formed by the sublimation thermal transfer method because it has excellent transparency, high reproducibility and gradation of neutral colors, and can easily form a high-quality image equivalent to a conventional full-color photographic image. Is widely done. The sublimation type thermal transfer method uses a thermal transfer sheet in which a colored layer containing a sublimation dye is provided on one surface of a base material (hereinafter, the base material provided in the thermal transfer sheet is referred to as a first base material), and a transferred body. This is a method of producing an image by heating from the back layer of a thermal transfer sheet and sublimating and transferring the sublimation dye contained in the coloring layer to the receiving layer to form an image.
Here, the thermal transfer image formed on the receiving layer by the sublimation type thermal transfer method is excellent in gradation, but the formed image is located on the outermost surface of the printed matter, so that it is inferior in durability such as scratch resistance. There is a problem that the formed image deteriorates with time.

In order to solve these problems, the transfer layer is transferred onto the image forming surface of the printed matter from the thermal transfer sheet provided with the transfer layer including the protective layer, and the durability of the printed matter is improved.

Further, as another method for producing a printed matter, an intermediate transfer medium receiving layer including a base material (hereinafter, the base material provided by the intermediate transfer medium is referred to as a second base material), a release layer, and a transferable receiving layer. A method is known in which an image is formed on a thermal transfer sheet or the like, and a release layer and a receptive layer are transferred from this intermediate transfer medium onto a transfer target.

Such imprints are used for identification cards, ID cards, etc., but in recent years, it is expensive to prevent bacteria such as Escherichia coli from breeding on these imprints and becoming a source of infection in medical settings. It may be required to have antibacterial properties.

Here, Patent Document 1 proposes to improve the durability and antibacterial property of a printed matter by transferring a transfer layer containing an inorganic antibacterial agent from a thermal transfer sheet onto the printed matter.

Japanese Unexamined Patent Publication No. 2012-71447

In the thermal transfer sheet disclosed in Patent Document 1, the present inventors do not have good adhesion between the base material and the transfer layer, and the transfer layer is peeled off from the base material when not heated, so-called. We have found a new problem that foil drop may occur.

Then, the present inventors have stated that the antibacterial property and the foil holding property of the thermal transfer sheet can be compatible with each other by setting the average particle size of the antibacterial particles contained in the release layer provided in the transfer layer and the content thereof within a specific numerical range. I got the knowledge of.
Further, by incorporating the antibacterial particles in the release layer provided in the intermediate transfer medium and keeping the average particle size and the content thereof within a specific numerical range, the antibacterial property and the foil holding property of the intermediate transfer medium are similarly compatible. I got the finding that it can be done.

Therefore, an object to be solved by the present invention is to provide a thermal transfer sheet and an intermediate transfer medium having high antibacterial properties and foil holding properties.
Another object of the present invention to be solved is to provide a printed matter produced by using the thermal transfer sheet or the intermediate transfer medium.
Another object to be solved by the present invention is to provide a method for producing a printed matter using the thermal transfer sheet or the intermediate transfer medium.
Further, an object to be solved by the present invention is to provide a printed matter manufacturing system for manufacturing the printed matter.

The thermal transfer sheet of the present invention
A first substrate and a transfer layer having at least a release layer are provided.
The release layer contains a resin material and antibacterial particles,
The average particle size of the antibacterial particles is 1 μm or more and 8 μm or less.
The release layer is characterized in that the content of the antibacterial particles with respect to 100 parts by mass of the resin material is 2.8 parts by mass or more and 8 parts by mass or less.

In one embodiment, the thickness of the release layer is 0.5 μm or more and 3 μm or less.

In one embodiment, the ratio of the average particle size of the antibacterial particles to the thickness of the release layer (average particle size of antibacterial particles / thickness of the release layer) is 1 or more and 8 or less.

In one embodiment, the antibacterial particles are phosphates that carry antibacterial metal ions.

In one embodiment, the release layer comprises an antistatic material.

The printed matter of the present invention is a printed matter produced by using the above-mentioned thermal transfer sheet.
It is characterized by including a transfer body and a transfer layer.

The method for producing a printed matter of the present invention is the above-mentioned method for producing a printed matter.
The process of preparing the thermal transfer sheet and the transfer target, and
The process of transferring the transfer layer of the thermal transfer sheet onto the transfer target, and
It is characterized by including.

In one embodiment, the method for producing a printed matter of the present invention includes a step of irradiating the transferred body with a sterilizing line after the transfer of the transfer layer.

The intermediate transfer medium of the present invention includes a second base material, a release layer, and a receiving layer.
The release layer contains a resin material and antibacterial particles,
The average particle size of the antibacterial particles is 1 μm or more and 8 μm or less.
The release layer is characterized in that the content of the antibacterial particles with respect to 100 parts by mass of the resin material is 2.8 parts by mass or more and 8 parts by mass or less.

The printed matter of the present invention is a printed matter produced by using the above-mentioned intermediate transfer medium.
It is characterized by including a transfer material, a peeling layer, and a receiving layer.

The method for producing a printed matter of the present invention is the above-mentioned method for producing a printed matter.
The step of preparing the intermediate transfer medium and the transfer target, and
The process of forming an image on the receiving layer of the intermediate transfer medium,
A step of transferring the release layer and the receiving layer of the intermediate transfer medium onto the transfer target, and
It is characterized by including.

In one embodiment, the method for producing a printed matter of the present invention includes a step of irradiating a transferred body with a sterilizing line after transferring the release layer and the receiving layer.

The printed matter manufacturing system of the present invention is for manufacturing the printed matter, and is characterized by including a thermal transfer printer and a sterilization mechanism.

According to the present invention, it is possible to provide a thermal transfer sheet and an intermediate transfer medium having high antibacterial properties and foil holding properties.
Further, according to the present invention, it is possible to provide a printed matter produced by using the thermal transfer sheet or the intermediate transfer medium.
Further, according to the present invention, it is possible to provide a method for producing a printed matter using the thermal transfer sheet or the intermediate transfer medium.
Further, according to the present invention, it is possible to provide a printed matter manufacturing system for manufacturing the printed matter.

It is the schematic sectional drawing which shows one Embodiment of the thermal transfer sheet of this invention. It is the schematic sectional drawing which shows one Embodiment of the thermal transfer sheet of this invention. It is the schematic sectional drawing which shows one Embodiment of the thermal transfer sheet of this invention. It is the schematic sectional drawing which shows one Embodiment of the intermediate transfer medium of this invention. It is schematic cross-sectional view which shows one Embodiment of the printed matter of this invention. It is schematic cross-sectional view which shows one Embodiment of the printed matter of this invention. It is schematic cross-sectional view which shows one Embodiment of the printed matter of this invention.

(Thermal transfer sheet)
As shown in FIG. 1, the thermal transfer sheet 10 according to the present invention includes a first base material 11 and a transfer layer 13 including at least a release layer 12. In the printed matter produced by using the thermal transfer sheet 10, the transfer layer 13 is located on the outermost surface.
Further, in one embodiment, as shown in FIG. 2, the transfer layer 13 includes an adhesive layer 14 on the outermost surface of the transfer layer.
Further, in one embodiment, as shown in FIG. 3, the thermal transfer sheet 10 includes a colored layer 15 so as to be surface-sequential with the transfer layer 13. As shown in FIG. 3, the thermal transfer sheet 10 may include a plurality of colored layers 15.
Further, in one embodiment, as shown in FIGS. 1 to 4, the thermal transfer sheet 10 includes a back surface layer 16 on a surface opposite to the surface of the first base material 11 on which the transfer layer 13 is provided.
Further, in one embodiment, the thermal transfer sheet 10 of the present invention may further include a release layer on the first base material (not shown).
Further, when the colored layer 15 is a melt transfer type colored layer, a second release layer may be provided between the first base material 11 and the colored layer 15 (not shown).
Hereinafter, each layer included in the thermal transfer sheet according to the present invention will be described.

(1st base material)
The first base material is particularly long as it has heat resistance that can withstand the thermal energy applied during thermal transfer, and has mechanical strength and solvent resistance that can support the transfer layer and the like provided on the first base material. Can be used without restrictions.

As the first base material, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), 1,4-polycyclohexylene methylene terephthalate, terephthalic acid-cyclohexanedimethanol-ethylene glycol co-weight. Combined polyester, polyamide such as nylon 6 and nylon 6,6, polyolefin such as polyethylene (PE), polypropylene (PP) and polymethylpentene, polyvinyl chloride, polyvinyl alcohol (PVA), polyvinyl acetate, vinyl chloride- Vinyl acetate copolymers, vinyl resins such as polyvinyl butyral and polyvinylpyrrolidone (PVP), (meth) acrylic resins such as polyacrylate, polymethacrylate and polymethylmethacrylate, imide resins such as polyimide and polyetherimide, cellophane, A film composed of a cellulose resin such as cellulose acetate, nitrocellulose, cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB), a styrene resin such as polystyrene (PS), a polycarbonate, and a resin material such as an ionomer resin. (Hereinafter, simply referred to as "resin film") can be used.
Among the above-mentioned resins, polyesters such as PET and PEN are preferable, and PET is particularly preferable, from the viewpoint of heat resistance and mechanical strength.
In the present invention, "(meth) acrylic" includes both "acrylic" and "methacryl". Further, "(meth) acrylate" includes both "acrylate" and "methacrylate".

Further, the above-mentioned laminated body of the resin film can also be used as the first base material. The laminate of the resin film can be produced by using a dry lamination method, a wet lamination method, an extraction method, or the like.

When the first base material is a resin film, the resin film may be a stretched film or an unstretched film, but from the viewpoint of strength, the stretched film is stretched in the uniaxial direction or the biaxial direction. It is preferable to use a film.

The thickness of the first base material is preferably 2 μm or more and 25 μm or less, and more preferably 3 μm or more and 16 μm or less. As a result, the mechanical strength of the first base material and the transfer of thermal energy during thermal transfer can be improved.

(Transfer layer)
The thermal transfer sheet of the present invention includes a transfer layer, and the transfer layer includes at least a release layer. In the present invention, the release layer is a layer arranged at a position closest to the first substrate of the transfer layer.
Further, in one embodiment, the transfer layer includes an adhesive layer on the release layer.

(Release layer)
The release layer is characterized by containing a resin material and antibacterial particles.
As the resin material, for example, polyester, polyamide, polyolefin, vinyl resin, (meth) acrylic resin, imide resin, cellulose resin, styrene resin, polycarbonate, ionomer resin and the like can be used, and among these, antibacterial particles are used. A (meth) acrylic resin is preferable because it has excellent dispersibility, excellent foil retention (also referred to as substrate adhesion) and foil breakability of the thermal transfer sheet.

The glass transition temperature (Tg) of the resin material is preferably 40 ° C. or higher and 130 ° C. or lower. Thereby, the plasticizer resistance of the printed matter can be improved.
In the present invention, the Tg of the resin material is a value obtained by differential scanning calorimetry (DSC) in accordance with JIS K 7121.

The content of the resin material in the release layer is preferably 50% by mass or more and 95% by mass or less, and more preferably 70% by mass or more and 90% by mass or less. Thereby, the foil holding property of the thermal transfer sheet can be further improved.

As the antibacterial particles, phosphates, zeolites, tovamorites and the like carrying antibacterial metal ions can be used. In the present invention, zeolite refers to an aluminosilicate having voids in the crystal structure, and tovamorite refers to crystalline calcium silicate hydrate.

Examples of the antibacterial metal ion include gold ion, silver ion, palladium ion, platinum ion, cadmium ion, cobalt ion, nickel ion, copper ion, zinc ion, tin ion and the like, and among these, the viewpoint of antibacterial property. From the above, silver ion, copper ion, nickel ion and zinc ion are preferable, and silver ion and zinc ion are particularly preferable.
Further, two or more kinds of antibacterial metal ions may be supported on the above phosphate or the like, and the release layer may contain two or more kinds of antibacterial particles.
The method for supporting the antibacterial metal ion is not particularly limited, and examples thereof include an ion exchange method and a silver mirror reaction.

Preferably, the antibacterial particles are a phosphate carrying silver ions, and particularly preferably a phosphate carrying silver ions and zinc ions.

The average particle size of the antibacterial particles is 1 μm or more and 8 μm or less, and more preferably 1.5 μm or more and 4.5 μm or less. Thereby, the foil holding property of the thermal transfer sheet can be improved. In addition, the plasticizer resistance of the printed matter produced by using the thermal transfer sheet of the present invention can be improved.
In the present invention, the average particle size of the antibacterial particles is measured as follows.
Using a scanning electron microscope (manufactured by Hitachi, Ltd., S-4700), an image of 5,000 times the transfer layer surface side of the thermal transfer sheet is taken. Differentiate between antibacterial particles and other particles by energy dispersive X-ray analysis. Using the image analysis software ImageJ, 20 antibacterial particles in the photograph are randomly selected, and the average value of the major axis of the primary particles is calculated.
The average particle of the antibacterial particles may be measured on the transfer layer transferred onto the transfer target.

In the release layer, the content of the antibacterial particles with respect to 100 parts by mass of the resin material is 1.8 parts by mass or more and 8 parts by mass or less. Thereby, the antibacterial property and the foil holding property of the thermal transfer sheet can be improved. Further, the plasticizer resistance of the printed matter can be improved.
The content of the antibacterial particles is preferably 2 parts by mass or more and 6 parts by mass or less, and more preferably 2 parts by mass or more and 4.5 parts by mass or less.

The release layer preferably contains an antistatic material. Thereby, the antibacterial property of the thermal transfer sheet can be improved. In addition, the amount of antibacterial particles used can be suppressed, and the foil holding property of the thermal transfer sheet can be improved. Further, the handleability of the printed matter to be manufactured can be improved.
High antistatic materials include, for example, quaternary ammonium salt-containing (meth) acrylate resin, polyethylene oxide, polyether ester amide, polyether amide imide, polyethylene oxide-epichlorohydrin copolymer, and polyether-polyolefin copolymer. Molecular antistatic materials and lows such as glycerin fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, alkyl sulfonates, alkyl benzene sulfonates, tetraalkyl ammonium salts, trialkyl benzyl ammonium salts and alkyl betaines. Examples include molecular type antistatic materials.
Among these, when the release layer contains a (meth) acrylic resin, a quaternary ammonium salt-containing (meth) acrylate resin is preferable from the viewpoint of dispersion stability in the release layer.
The release layer may contain two or more types of antistatic materials.

In the release layer, the content of the antistatic material with respect to 100 parts by mass of the resin material is preferably 0.1 part by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less. Thereby, the antibacterial property and the foil holding property of the thermal transfer sheet can be further improved. In addition, the handleability of the printed matter can be further improved.

Further, the release layer may contain additives such as a filler, a plastic material, an ultraviolet absorber, an inorganic particle, an organic particle, a mold release material and a dispersant as long as the characteristics of the present invention are not impaired.

The thickness of the release layer is preferably 0.5 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less. Thereby, the antibacterial property and the foil holding property of the thermal transfer sheet can be further improved. In addition, the transferability of the transfer layer can be improved.

The ratio of the average particle size of the antibacterial particles to the thickness of the release layer (average particle size of antibacterial particles / thickness of the release layer) is preferably 1 or more and 8 or less, preferably 1.5 or more and 6.5 or less. More preferably. Thereby, the antibacterial property and the foil holding property of the thermal transfer sheet can be further improved. In addition, the plasticizer resistance of the printed matter can be improved.

The release layer is formed by dispersing or dissolving the above material in water or an appropriate solvent and using known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod coating method. , A coating film is formed by applying it on a first base material or the like, and this can be formed by drying.

(Adhesive layer)
In one embodiment, the transfer layer included in the thermal transfer sheet of the present invention includes an adhesive layer.
The adhesive layer contains at least one type of thermoplastic resin that is softened by heating and exhibits adhesiveness.
Examples of the thermoplastic resin include polyester, vinyl resin, (meth) acrylic resin, (meth) acrylic resin, polyurethane, cellulose resin, polyamide, polyolefin, polystyrene, and chlorinated resins thereof.

The adhesive layer may contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

The thickness of the adhesive layer is not particularly limited, but can be 0.1 μm or more and 2 μm or less.

The adhesive layer is formed by dispersing or dissolving the above-mentioned material in water or an appropriate solvent, and using known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod coating method. , A coating film is formed by applying it on a release layer or the like, and this can be formed by drying.

(Colored layer)
The thermal transfer sheet includes a coloring layer containing a coloring material on the first base material so as to be surface-sequential with the transfer layer. The thermal transfer sheet may include a plurality of colored layers.
The colored layer may be a sublimation transfer type colored layer to which only the sublimation dye contained in the colored layer is transferred, or may be a melt transfer type colored layer to which the colored layer itself is transferred.

The colored layer contains at least one colorant, which may be a pigment or a dye. Moreover, the dye may be a sublimation dye.
Examples of coloring materials include carbon black, acetylene black, lamp black, black smoke, iron black, aniline black, silica, calcium carbonate, titanium oxide, cadmium red, cadmopone red, chrome red, vermilion, red iron oxide, and azo pigments. Alizarin Lake, Kinakridon, Cochineal Lake Perylene, Yellow Oaker, Aureolin, Cadmium Yellow, Cadmium Orange, Chrome Yellow, Zink Yellow, Naples Yellow, Nickel Yellow, Azo Dyes, Greenish Yellow, Ultramarine, Rocks Blue, Cobalt, Phthalocyanin , Anthracinone, indicoid, cinnabar green, cadmium green, chrome green, phthalocyanine, azomethine, perylene, aluminum pigment, as well as diarylmethane dye, triarylmethane dye, thiazole dye, merocyanine dye, pyrazolone dye, methine dye, indoaniline dye Sublimation properties of acetophenone azomethine dyes, pyrazoloazomethine dyes, xanthene dyes, oxazine dyes, thiazine dyes, azine dyes, acrydin dyes, azo dyes, spiropyran dyes, indolinospiropirane dyes, fluorane dyes, naphthoquinone dyes, anthraquinone dyes and quinophthalone dyes Examples include dyes.

In one embodiment, the colored layer comprises a resin material, and examples thereof include polyester, polyamide, polyolefin, vinyl resin, (meth) acrylic resin, cellulose resin, styrene resin, polycarbonate, butyral resin, phenoxy resin, ionomer resin and the like. Be done.
Further, the colored layer may contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

The thickness of the colored layer is not particularly limited, and can be, for example, 0.1 μm or more and 3 μm or less.

The colored layer is formed by dispersing or dissolving the above material in water or an appropriate solvent and using known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod coating method. , It can be formed by applying it on the first base material to form a coating film and drying it.

(Release layer)
In one embodiment, the thermal transfer sheet of the present invention comprises a release layer between the first substrate and the transfer layer. Thereby, the transferability of the thermal transfer sheet can be improved.

In one embodiment, the release layer contains a resin material, and examples thereof include (meth) acrylic resin, polyurethane, polyamide, polyester, melamine resin, polyol resin, cellulose resin, and silicone resin.

Further, in one embodiment, the release layer includes a release material such as a silicone oil, a phosphoric acid ester-based plastic material, a fluorine-based compound, a wax, a metal soap, and a filler.

The thickness of the release layer is not particularly limited, and can be, for example, 0.2 μm or more and 2 μm or less.

The release layer is a known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod coating method by dispersing or dissolving the above material in water or an appropriate solvent. Therefore, it can be formed by applying it on a first base material or the like to form a coating film and drying it.

(Second release layer)
In one embodiment, the thermal transfer sheet of the present invention includes a second release layer between the melt transfer type colored layer and the first substrate.
The second release layer contains a resin material, and examples thereof include polyester, polyamide, polyolefin, vinyl resin, (meth) acrylic resin, imide resin, cellulose resin, styrene resin, polycarbonate and ionomer resin.

The content of the resin material in the second release layer is preferably 50% by mass or more and 95% by mass or less, and more preferably 70% by mass or more and 90% by mass or less. Thereby, the transferability of the colored layer can be improved.

Further, the second release layer may contain additives such as a filler, a plastic material, an ultraviolet absorber, inorganic particles, organic particles, a mold release material and a dispersant as long as the characteristics of the present invention are not impaired. ..

The thickness of the release layer is preferably 0.5 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less. Thereby, the transferability of the colored layer can be improved.

The release layer is formed by dispersing or dissolving the above material in water or an appropriate solvent and using known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod coating method. , A coating film is formed by applying it on a first base material or the like, and this can be formed by drying.

(Back layer)
In one embodiment, the thermal transfer sheet of the present invention includes a back layer on the surface of the first base material on which the transfer layer is not provided. This makes it possible to prevent sticking and wrinkles due to heating during thermal transfer.

In one embodiment, the back layer contains a resin material, and examples thereof include cellulose resin, styrene resin, vinyl resin, polyester, polyurethane, silicone-modified polyurethane, fluorine-modified polyurethane, and (meth) acrylic resin.

Further, in one embodiment, the back layer contains a two-component curable resin as a resin material, which is cured by being used in combination with an isocyanate compound or the like. Examples of such a resin include polyvinyl acetals such as polyvinyl acetal and polyvinyl butyral.

In one embodiment, the back layer comprises inorganic or organic particles. As a result, sticking and wrinkles due to heating during thermal transfer can be further prevented.

Examples of the inorganic particles include clay minerals such as talc and kaolin, carbonates such as calcium carbonate and magnesium carbonate, hydroxides such as aluminum hydroxide and magnesium hydroxide, sulfates such as calcium sulfate, and oxides such as silica. , Graphite, sulphate, and inorganic particles such as boron hydroxide.
The organic particles include (meth) acrylic resin, Teflon (registered trademark) resin, silicone resin, lauroyl resin, phenol resin, acetal resin, styrene resin, polyamide, and other organic resin particles, or these are reacted with a cross-linking material. Examples thereof include crosslinked resin particles.

The thickness of the back layer is preferably 0.1 μm or more and 2 μm or less, and more preferably 0.1 μm or more and 1 μm or less. As a result, it is possible to prevent sticking, wrinkles, and the like while maintaining the transmissibility of thermal energy during thermal transfer.

The back layer is formed by dispersing or dissolving the above material in water or a suitable solvent and using known means such as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod coating method. , It can be formed by applying it on the first base material to form a coating film and drying it.

(Intermediate transfer medium)
As shown in FIG. 4, the intermediate transfer medium 20 of the present invention is characterized by including a second base material 21, a release layer 22, and a receiving layer 23.
Further, in one embodiment, the intermediate transfer medium 20 may include a protective layer between the release layer 22 and the receiving layer 23 (not shown). Further, in one embodiment, the intermediate transfer medium 20 may include an intermediate layer between the protective layer and the release layer (not shown).
Hereinafter, each layer included in the intermediate transfer medium of the present invention will be described.

(Second base material)
As the second base material, a material that can be used for the first base material can be appropriately used.

(Release layer)
The intermediate transfer medium comprises a release layer containing a resin material and antibacterial particles.
Since the preferable structure of the release layer is the same as that of the thermal transfer sheet, the description thereof is omitted here.

(Receptive layer)
The receiving layer is a layer that receives the sublimation dye transferred from the dye layer included in the thermal transfer sheet and maintains the formed image, and contains at least one resin material. Examples of the resin material include epoxy resin, polyester, polyamide, polyolefin, vinyl resin, (meth) acrylic resin, imide resin, cellulose resin, styrene resin, polycarbonate, ionomer resin and the like.

The content of the resin material in the receiving layer is not particularly limited, and can be, for example, 80% by mass or more and 98% by mass or less.

In one embodiment, the receiving layer comprises one or more release materials. As a result, the releasability from the thermal transfer sheet after image formation can be improved.
Examples of the release material include solid waxes such as polyethylene wax and amide wax, fluorine-based surfactants, phosphoric acid ester-based surfactants, silicone oils, reactive silicone oils, curable silicone oils, and silicone resins. Be done.

The content of the release material in the receiving layer is preferably 0.5% by mass or more and 20% by mass or less, and more preferably 0.5% by mass or more and 10% by mass or less. As a result, the releasability from the thermal transfer sheet after image formation can be further improved.

In addition, the receiving layer may contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

The thickness of the receiving layer is not particularly limited, and can be 0.5 μm or more and 20 μm or less.

The receiving layer disperses or dissolves the above-mentioned material in water or a suitable solvent to prepare a coating liquid, which is used as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod. It can be formed by applying it on a release layer or the like to form a coating film by a known means such as a coating method, and drying the coating film.

(Protective layer)
In one embodiment, the intermediate transfer medium of the present invention comprises a protective layer between the release layer and the receptive layer.

The protective layer contains a resin material, and examples thereof include polyester, (meth) acrylic resin, epoxy resin, styrene resin, polyurethane, ionizing thermosetting resin, and ultraviolet absorbing resin. Among these, polyester is preferable from the viewpoint of durability of the printed matter to be produced and foil breakability.

In the present invention, the Tg of polyester is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 55 ° C. or higher and 70 ° C. or lower. As a result, the durability of the manufactured printed matter can be further improved, and the foil breakability and the transport wrinkle prevention property can be improved.

The number average molecular weight (Mn) of the polyester is preferably 2000 or more and 25,000 or less, and more preferably 8000 or more and 20000 or less. As a result, the durability of the intermediate transfer medium can be further improved, and the foil breakability thereof can be improved.
In the present invention, Mn of the resin means a value measured by gel permeation chromatography using polystyrene as a standard substance, and is measured by a method according to JIS K 7252-1.

The content of polyester in the protective layer is preferably 50% by mass or more and 99.5% by mass or less, and more preferably 70% by mass or more and 98% by mass or less. As a result, the durability of the manufactured printed matter can be further improved, and the foil breakability and the transport wrinkle prevention property can be improved.

In one embodiment, the protective layer comprises a filler.
The filler may be an organic filler or an inorganic filler, and these may be used in combination.
Examples of the organic filler include resins such as melamine resin, benzoguanamine resin, (meth) acrylic resin, polyamide, fluororesin, phenol resin, styrene resin, polyolefin, silicone resin, and copolymers of monomers constituting these resins. Examples include particles (resin particles). Among these, particles made of (meth) acrylic resin are particularly preferable from the viewpoint of durability.
Inorganic fillers include clay minerals such as talc and kaolin, carbonates such as calcium carbonate and magnesium carbonate, hydroxides such as aluminum hydroxide and magnesium hydroxide, sulfates such as calcium sulfate, and oxides such as silica. , Graphite, sulphate, boron nitride and the like.

Further, the surface of the filler may be treated with a surface treatment material such as a silane coupling agent.

The average particle size of the filler is preferably 3.8 μm or less, more preferably 3.5 μm or less. Thereby, the transfer wrinkle prevention property of the intermediate transfer medium can be improved.
In the present invention, the average particle size means the volume average particle size, and is measured according to JIS Z 8819-2.

The content of the filler in the protective layer is 0.5% by mass or more and 5% by mass or less, preferably 0.7% by mass or more and 4.7% by mass or less, and 1% by mass or more and 4.5% by mass or less. Is more preferable. Thereby, the transfer wrinkle prevention property of the intermediate transfer medium can be improved.

To the extent that the properties of the present invention are not impaired, the protective layer comprises polyester, polyamide, polyolefin, vinyl resin, polyvinyl acetal, (meth) acrylic resin, imide resin, cellulose resin, styrene resin, polycarbonate and ionomer having a Tg of less than 45 ° C. Other resin materials such as resin and the above-mentioned additives can be included.

The thickness of the protective layer is preferably 0.5 μm or more and 4.5 μm or less, and more preferably 1 μm or more and 3 μm or less. As a result, the durability of the printed matter to be manufactured can be further improved.

The protective layer is prepared by dispersing or dissolving the above material in water or a suitable solvent to obtain a coating liquid, which is used as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod. It can be formed by applying it on a release layer or the like to form a coating film by a known means such as a coating method, and drying the coating film.

(Middle layer)
In one embodiment, the intermediate transfer medium includes an intermediate layer between the protective layer and the release layer, which can further improve the durability of the printed matter to be produced.

In one embodiment, the intermediate layer contains a resin material, and examples thereof include polyester, (meth) acrylic resin, epoxy resin, styrene resin, polyurethane, ionizing thermosetting resin, and ultraviolet absorbing resin.

In a preferred embodiment, the intermediate layer contains at least one (meth) acrylic polyol resin having a glass transition temperature (Tg) of 80 ° C. or higher.
The Tg of the (meth) acrylic polyol resin is preferably 80 ° C. or higher and 110 ° C. or lower, and more preferably 85 ° C. or higher and 105 ° C. or lower. Thereby, the durability of the intermediate transfer medium can be further improved.

In the present invention, the (meth) acrylic polyol resin means a resin containing at least one (meth) acrylic acid ester having a hydroxy group as a polymerization component.
Examples of the (meth) acrylic acid ester having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth). ) Acrylate and the like can be mentioned.
The content of the (meth) acrylic acid ester having a hydroxy group in the (meth) acrylic polyol resin is preferably 8% by mass or more, more preferably 10% by mass or more, based on all the constituent units. Thereby, the durability of the intermediate transfer medium can be further improved.

The (meth) acrylic polyol resin may contain one or more monomers other than the (meth) acrylic acid ester as a polymerization component, and may contain, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth). (Meta) acrylic acid alkyl esters such as meta) acrylate, 2-ethylhexyl (meth) acrylate and octyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, acrylamide, metaacrylamide, vinyl acetate, maleic anhydride and the like. Can be mentioned.

The hydroxyl value of the (meth) acrylic polyol resin is preferably in the range of 10 mgKOH / g or more and 100 mgKOH / g or less. As a result, the durability of the intermediate transfer medium can be further improved, the foil breaking property thereof can be improved, and the occurrence of tailing and the like can be prevented.
In the present invention, the "hydroxyl value" of the acrylic polyol resin means the number of mg of potassium hydroxide required to acetylate the hydroxyl group contained in 1 g of the (meth) acrylic polyol resin. The hydroxyl value conforms to JIS K 0070, the acrylic polyol resin is made into a pyridine solution containing acetic anhydride, the hydroxyl group is acetylated, the excess acetylation reagent is hydrolyzed with water, and the generated acetic acid is potassium hydroxide. It can be obtained by performing titration with.

The weight average molecular weight (Mw) of the (meth) acrylic polyol resin is preferably 8,000 or more and 70,000 or less, and more preferably 10,000 or more and 50,000 or less. As a result, the durability of the intermediate transfer medium can be further improved, and the foil breakability thereof can be improved.
In the present invention, Mw of the resin means a value measured by gel permeation chromatography using polystyrene as a standard substance, and is measured by a method according to JIS K 7252-1.

The (meth) acrylic polyol resin is preferably a curable (meth) acrylic polyol resin obtained by curing a (meth) acrylic polyol resin having a Tg of 80 ° C. or higher with a curing material. Thereby, the durability of the intermediate transfer medium can be further improved.

Examples of the curing material include metal chelating materials such as aliphatic amine compounds, cyclic aliphatic amine compounds, aromatic amine compounds, titanium chelating materials, zirconium chelating materials and aluminum chelating materials, acid anhydrides and isocyanate compounds. ..

When the curing material is an isocyanate compound, the molar equivalent ratio (-NCO / -OH) of the isocyanate group contained in the compound and the hydroxyl group contained in the (meth) acrylic polyol resin is preferably 0.2 or more and 3 or less. , 0.3 or more and 2 or less is more preferable. Thereby, the foil breakability can be improved.

The content of the (meth) acrylic polyol resin in the intermediate layer is preferably 50% by mass or more and 99% by mass or less, and more preferably 70% by mass or more and 95% by mass or less. As a result, the durability of the intermediate transfer medium can be further improved, and the foil breakability thereof can be improved.

Further, the intermediate layer may contain the above-mentioned additive as long as the characteristics of the present invention are not impaired.

The thickness of the intermediate layer is preferably 0.5 μm or more and 5 μm or less, and more preferably 1 μm or more and 4 μm or less. As a result, the durability of the intermediate transfer medium can be further improved, and the foil breakability thereof can be improved.

In the intermediate layer, the above material is dispersed or dissolved in water or a suitable solvent to prepare a coating liquid, which is used as a roll coating method, a reverse roll coating method, a gravure coating method, a reverse gravure coating method, a bar coating method and a rod. It can be formed by applying it on the release layer by a known means such as a coating method to form a coating film, and drying the coating film.

(Printed matter)
In one embodiment, the printed matter 30 of the present invention is manufactured by using the thermal transfer sheet, and includes a transferred body 31 and a transfer layer 13 including a release layer 12, as shown in FIG. It is characterized by that.
As shown in FIG. 5, the transferred body 31 may be composed of only the transferred body base material 32, and as shown in FIG. 6, it is composed of the transferred body base material 32 and the receiving layer 33. It may be what is done.

(Subject base material)
The base material to be transferred is not particularly limited, and it is preferable to change it as appropriate according to each application. For example, high-quality paper, art paper, coated paper, natural fiber paper, tracing paper, resin-coated paper. , Paper base materials such as cast-coated paper, paperboard, synthetic paper and impregnated paper, ID cards, card base materials used in the field of IC cards, glass, metal, ceramics, wood, cloth and the like. It is not limited to this.
Examples of the card base material include a resin sheet molded from a polyvinyl chloride resin, a vinyl chloride-vinyl acetate copolymer, polycarbonate, a polyester resin, and the like, a metal sheet, and the like. The thickness of the card base material may be appropriately determined according to the intended use of the finally formed printed matter.

The thickness of the substrate to be transferred is not particularly limited, and is preferably changed as appropriate according to the intended use, but can be, for example, 30 μm or more and 900 μm or less.

(Receptive layer)
In one embodiment, as shown in FIG. 6, the transferred body 31 may include a receiving layer 33 on the transferred body base material 32. Since the preferable structure of the receiving layer is the same as that of the intermediate transfer medium, the description thereof is omitted here.
The receiving layer may have an image formed on it.

The thickness of the receiving layer is preferably 1 μm or more and 10 μm or less.

(Transfer layer)
Since the composition and thickness of the transfer layer included in the printed matter have been described above, the description thereof will be omitted here.

The area ratio (protruding area ratio) of the protruding portion of the antibacterial particles in the peeling layer provided in the printed matter is preferably 0.05% or more and 3% or less, and 0.1% or more and 1% or less. More preferably. Thereby, the antibacterial property of the printed matter can be improved.
In the present invention, the protruding area ratio of the antibacterial particles in the peeling layer is determined by observing the peeling layer provided in the printed matter by using a non-contact surface measuring device VertScan (manufactured by Ryoka System Co., Ltd.) using a light interference method. , Can be calculated as the ratio of the surface area of the exposed antibacterial particles to the total observed area.

In one embodiment, the imprint 40 of the present invention is produced by using the intermediate transfer medium, and as shown in FIG. 6, the transferred body base material (transferred body) 41 and the receiving layer 23 , The peeling layer 22 is provided.
Further, in one embodiment, the imprint 40 is provided with a protective layer between the receiving layer 23 and the peeling layer 22 (not shown).
Since the details of the substrate to be transferred, the receiving layer, the peeling layer, and the protective layer provided in the printed matter produced by using the intermediate transfer medium have been described above, the description thereof will be omitted here.

(Manufacturing method of printed matter)
In one embodiment, the method for producing a printed matter of the present invention is:
The process of preparing the thermal transfer sheet and the transfer target, and
The process of transferring the transfer layer of the thermal transfer sheet onto the transfer target, and
It is characterized by including.
In one embodiment, the method for producing a printed matter of the present invention includes a step of irradiating the transferred body with a sterilizing line after the transfer of the transfer layer.
In one embodiment, the method for producing a printed matter of the present invention further comprises the step of forming an image on the transferred object before the transfer of the transfer layer.

(Step of preparing the thermal transfer sheet and the transferred body)
Since the method for manufacturing the thermal transfer sheet has been described above, the description thereof is omitted here.
As the transfer material, a commercially available product may be used. Further, a transfer material base material prepared by a method such as a T-die method or an inflation method may be used, and a coating liquid for forming a receiving layer is applied and dried on the transfer material base material. The transferred product obtained in the above method may be used. Further, a laminate obtained by dry-laminating a substrate to be transferred made of a different material may be used.

(Transfer process of transfer layer)
The method for producing a printed matter of the present invention includes a step of transferring a transfer layer from the thermal transfer sheet. The transfer of the transfer layer is preferably performed after the image is formed on the transfer target.

(Irradiation process of sterilization line)
In one embodiment, the method for producing a printed matter of the present invention includes a step of irradiating the transferred body with a sterilizing line after the transfer of the transfer layer.
In one embodiment, a germicidal lamp is arranged near the discharge port of the thermal transfer printer, thereby irradiating the transferred object with a germicidal line.
Examples of the light source that can be used as a germicidal lamp include a high-pressure mercury lamp, an ultraviolet fluorescent lamp, and a xenon lamp.

(Image formation process)
In one embodiment, the method for producing a printed matter of the present invention further comprises the step of forming an image on the transferred object before the transfer of the transfer layer. When the colored layer is provided so as to be surface-sequential to the transfer layer, the image formation may be performed using the thermal transfer sheet of the present invention, or may be performed using a different thermal transfer sheet.

(Manufacturing method of printed matter)
In one embodiment, the method for producing a printed matter of the present invention is:
The step of preparing the intermediate transfer medium and the transfer target, and
The process of forming an image on the receiving layer of the intermediate transfer medium,
A step of transferring the release layer and the receiving layer of the intermediate transfer medium onto the transfer target, and
It is characterized by including.
In one embodiment, the method for producing a printed matter of the present invention includes a step of irradiating a transferred body with a sterilizing line after transferring the release layer and the receiving layer.

(Step of preparing the intermediate transfer medium and the transfer target)
Since the method for producing the intermediate transfer medium has been described above, the description thereof is omitted here.
Further, the transferred body may be one produced by the above-mentioned method, or a commercially available one may be used.

(Image formation process)
The method for producing a printed matter of the present invention includes a step of forming an image on a receiving layer included in an intermediate transfer medium.
The method of forming an image on the receiving layer is not particularly limited, and a conventionally known method can be used. For example, a thermal transfer sheet provided with a colored layer can be used.

(Transfer step of peeling layer and receiving layer)
The method for producing a printed matter of the present invention includes a step of transferring a release layer and a receiving layer from the intermediate transfer medium onto a transfer target. If the intermediate transfer medium is provided with a protective layer between the release layer and the receiving layer, this can also be transferred together.

(Irradiation process of sterilization line)
The step is as described above, and the description thereof is omitted here.

(Printed matter manufacturing system)
The printed matter manufacturing system of the present invention is characterized by including a thermal transfer printer and a sterilization mechanism.

(Thermal transfer printer)
The thermal transfer printer provided in the printed matter manufacturing system of the present invention is not particularly limited as long as it can carry the thermal transfer sheet or the intermediate transfer medium and can manufacture the printed matter, and is conventionally known. A thermal transfer printer can be used.

(Sterilization mechanism)
As a sterilization mechanism, a germicidal lamp can be used, and this can be provided by arranging the germicidal lamp near the discharge port of the thermal transfer printer.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1
A 4.5 μm-thick PET film was prepared as the first base material, and coating liquids A, B, and C for forming a colored layer having the following composition were sequentially applied to one surface thereof, dried, and each had a thickness. Colored layers A to C having a size of 0.7 μm were formed.
<Coating liquid A for forming a colored layer>
・ Disperse Yellow 2014 4 parts by mass ・ Polyvinyl acetal 3.5 parts by mass (Sekisui Chemical Co., Ltd., Eslek (registered trademark) KS-5)
-Polyethylene wax 0.1 parts by mass-Methyl ethyl ketone (MEK) 45 parts by mass-Toluene 45 parts by mass <Coating liquid B for forming a colored layer>
・ Disperse Thread 60 1.5 parts by mass ・ Disperse Bio Red 26 2 parts by mass ・ Polyvinyl acetal 4.5 parts by mass (Sekisui Chemical Co., Ltd., Eslek (registered trademark) KS-5)
-Polyethylene wax 0.1 parts by mass-MEK 45 parts by mass-Toluene 45 parts by mass <Coating liquid C for forming a colored layer>
・ Solvent Blue 63 4 parts by mass ・ Polyvinyl acetal 3.5 parts by mass (Sekisui Chemical Co., Ltd., Eslek (registered trademark) KS-5)
・ Polyethylene wax 0.1 parts by mass ・ MEK 45 parts by mass ・ Toluene 45 parts by mass

A coating dispersion liquid for forming a release layer having the following composition was applied and dried so as to be surface-sequential with the colored layer formed as described above to form a release layer having a thickness of 1 μm.
<Coating liquid for forming a release layer>
(Meta) acrylic resin 100 parts by mass (Soken Chemical Co., Ltd., Thermolac Lp-45M-30, Tg 105 ° C)
-Antibacterial particle A 3 parts by mass (manufactured by Fuji Chemical Co., Ltd., Bactekiller (registered trademark) BM-102NSC, average particle size 2 μm, silver ion / zinc ion-supported phosphate)
・ MEK 250 parts by mass ・ Toluene 250 parts by mass

On the release layer formed as described above, a coating liquid for forming an adhesive layer having the following composition was applied and dried to form an adhesive layer having a thickness of 1 μm.
<Coating liquid for forming an adhesive layer>
10 parts by mass of polyester (manufactured by Toyobo Co., Ltd., Byron (registered trademark) 226, Tg65 ° C, Mn8000)
・ 10 parts by mass of UV-absorbing acrylic resin (manufactured by Otsuka Chemical Co., Ltd., PUVA-50M-40TM, solid content 40%)
・ MEK 40 parts by mass ・ Toluene 40 parts by mass

A coating liquid for forming a back layer having the following composition was applied to the other surface of the PET film and dried to form a back layer having a thickness of 1 μm to obtain a thermal transfer sheet.
<Coating liquid for back layer>
-Polyvinyl butyral 2 parts by mass (Sekisui Chemical Co., Ltd., Eslek (registered trademark) BX-1)
-Polyisocyanate 9.2 parts by mass (manufactured by DIC Corporation, Burnock (registered trademark) D750)
-Phosphate ester-based surfactant 1.3 parts by mass (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Prysurf (registered trademark) A208N)
-Talc 0.3 parts by mass (manufactured by Nippon Talc Industry Co., Ltd., Micro Ace (registered trademark) P-3)
・ Toluene 43.6 parts by mass ・ MEK 43.6 parts by mass

Examples 2 to 7 and Comparative Examples 1 to 4
A thermal transfer sheet was produced in the same manner as in Example 1 except that the composition of the release layer and the thickness of the release layer were changed as shown in Table 1.
The details of each component in Table 1 are as follows.
-Antibacterial particles B: manufactured by Fuji Chemical Co., Ltd., Bactekiller (registered trademark) BM-102GA (IZ), average particle diameter 5 μm, silver ion / zinc ion-supported phosphate / antibacterial particles C: manufactured by Fuji Chemical Co., Ltd., Bactekiller® BM-45M-30, average particle size 10 μm, silver ion / zinc ion carrying phosphate

Example 8
A thermal transfer was prepared in the same manner as in Example 1 except that a coating liquid for forming a release layer having the following composition was used.
<Coating liquid for forming a release layer>
(Meta) acrylic resin 100 parts by mass (Soken Chemical Co., Ltd., Thermolac Lp-45M-30, Tg 105 ° C)
-Antibacterial particle A 3 parts by mass (manufactured by Fuji Chemical Co., Ltd., BM-102NSC, average particle diameter 2 μm)
-Antistatic material 5 parts by mass (manufactured by Taisei Fine Chemicals Co., Ltd., Acryt (registered trademark) 1SX-1071I, quaternary ammonium salt-containing (meth) acrylate resin)
・ MEK 250 parts by mass ・ Toluene 250 parts by mass

Example 9
A thermal transfer sheet was produced in the same manner as in Example 8 except that the structure of the release layer was changed as shown in Table 1.

Example 10
As the second base material, a PET film having a thickness of 12 μm (manufactured by Toray Co., Ltd., Lumirror (registered trademark) 12F65K) was prepared. A coating liquid for forming a release layer having the following composition was applied to one surface of the PET film and dried to form a release layer having a thickness of 1 μm.
<Coating liquid for forming a release layer>
80 parts by mass of (meth) acrylic resin (manufactured by Mitsubishi Chemical Corporation, Dianal (registered trademark) BR-87, Tg105 ° C, Mw25000)
・ 5 parts by mass of polyester (manufactured by Toyobo Co., Ltd., Byron (registered trademark) 200)
-Antibacterial particle A 3 parts by mass (manufactured by Fuji Chemical Co., Ltd., BM-102NSC, average particle diameter 2 μm)
-Antistatic material 5 parts by mass (manufactured by Taisei Fine Chemicals Co., Ltd., Acryt (registered trademark) 1SX-1071I, quaternary ammonium salt-containing (meth) acrylate resin)
・ Polyethylene wax 5 parts by mass (manufactured by Toyo Adre Co., Ltd., polywax 1000)
・ Toluene 192.5 parts by mass ・ MEK 192.5 parts by mass

An intermediate layer forming coating liquid having the following composition was applied onto the peeling layer and dried to form an intermediate layer having a thickness of 2 μm.
<Coating liquid for forming an intermediate layer>
100 parts by mass of (meth) acrylic polyol resin (manufactured by Taisei Fine Chemicals Co., Ltd., 6KW-700, solid content 36.5%, Tg 102 ° C., Mw55000, hydroxyl value 30.1)
-Isocyanate compound 3.6 parts by mass (manufactured by Mitsui Chemicals, Inc., Takenate (registered trademark) D110N, solid content 75%)
・ MEK 92 parts by mass

A coating liquid for forming a protective layer having the following composition was applied onto the intermediate layer and dried to form a protective layer having a thickness of 2 μm.
<Coating liquid for forming a protective layer>
・ Polyester 78.4 parts by mass
(Manufactured by Toyobo Co., Ltd., Byron (registered trademark) 200, Tg67 ° C, Mn17000)
-1.6 parts by mass of filler (manufactured by Nippon Shokubai Co., Ltd., Epostal (registered trademark) MA1002, average particle size 2 μm, (meth) acrylic resin particles)
・ MEK 20 parts by mass

A coating solution for forming a receiving layer having the following composition was applied onto the intermediate layer and dried to form a receiving layer having a thickness of 2 μm to obtain an intermediate transfer medium.
<Coating liquid for forming a receptive layer>
-95 parts by mass of vinyl chloride-vinyl acetate copolymer (manufactured by Nissin Chemical Industry Co., Ltd., Solveine (registered trademark) CNL)
・ Epoxy modified silicone oil 5 parts by mass (manufactured by Shin-Etsu Chemical Co., Ltd., KP-1800U)
・ 200 parts by mass of toluene ・ 200 parts by mass of MEK

<< Antibacterial evaluation >>
Using the colored layer of the thermal transfer sheet obtained in Examples 1 to 9 and Comparative Examples 1 to 4 and the following thermal transfer printer, a polyvinyl chloride card (manufactured by Dai Nippon Printing Co., Ltd., width 5 cm x length) was used as a transfer material. 7 cm) was prepared, and a black image (image gradation 0/255) was formed on the prepared.
The transfer layer included in the thermal transfer sheets obtained in the above Examples and Comparative Examples was transferred onto this image using the following thermal transfer printer to obtain a printed matter.
(Thermal transfer printer)
-Thermal head: Kyocera Corporation, KEE-57-12GAN2-STA
-Average resistance value of heating element: 3303Ω
-Main scanning direction resolution: 300 dpi (dot per inch)
-Secondary scanning direction resolution: 300 dpi
-Line speed: 3.0 msec. / Line
-Printing start temperature: 35 ° C
-Pulse duty ratio: 70%

Further, using the intermediate transfer medium obtained in Example 10, the thermal transfer sheet obtained in Example 1, and the thermal transfer printer, the colored layer A provided by the thermal transfer sheet is placed on the receiving layer provided by the intermediate transfer medium. The sublimation dye was transferred from ~ C to form a black image (image gradation 0/255).
The above-mentioned polyvinyl chloride card was prepared, and the transfer layer provided with the receiving layer on which the image was formed was transferred from the intermediate transfer medium onto the polyvinyl chloride card using a card laminator to obtain a printed matter.

The antibacterial property of the obtained printed matter was evaluated in accordance with JIS Z 2801 (film adhesion method).
Specifically, a bacterial solution containing 105 Escherichia coli was dropped onto the surface of the transfer layer provided on the printed matter, a PE film was adhered thereto, and the mixture was allowed to stand at 35 ° C. for 24 hours.
After standing, the cells adhering to the PE film and the laminate were washed out with SCDLP medium, the washing solution was collected, transferred to a petri dish, cultured at 35 ° C. for 45 hours, and then the viable cell count of Escherichia coli was measured. I counted.
The viable cell counts of Escherichia coli of the printed matter prepared by using the thermal transfer sheet provided with the release layer containing no antibacterial particles obtained in Comparative Example 1 were obtained in Examples 1 to 9 and Comparative Examples 2 to 4. Let y be the viable cell count of Escherichia coli in the printed matter prepared using the thermal transfer sheet and the intermediate transfer medium obtained in Example 10, determine the antibacterial activity value by the following formula (1), and based on the following evaluation criteria. evaluated. The evaluation results are summarized in Table 1.
Antibacterial activity value = logx / y (1)
(Evaluation criteria)
A: The antibacterial activity value was 2.7 or more.
B: The antibacterial activity value was 2 or more and less than 2.7.
NG: The antibacterial activity value was less than 2.

<< Evaluation of foil retention >>
The transfer layer forming portion of the thermal transfer sheet (intermediate transfer medium in Example 10) obtained in Examples and Comparative Examples was folded once in the longitudinal direction and once in the lateral direction and allowed to stand. After standing, the product was unfolded, visually observed, and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
(Evaluation criteria)
A: The foil drop of the transfer layer was less than ^{4 mm 2.}
B: The foil drop of the transfer layer was 4 mm ² or more and less ^{than 10 mm 2.} NG: The foil drop of the transfer layer was 10 mm ² or more.

<< Plasticizer resistance evaluation >>
A transfer layer provided with the printed matter obtained in the above antibacterial property evaluation and a soft vinyl chloride sheet containing a plasticizer (manufactured by Mitsubishi Chemical Corporation, Altron (registered trademark) # 480, thickness 400 μm), The soft vinyl chloride sheets containing a plasticizer were laminated so as to face each other, ^{a load of 24 g / cm 2} was applied, and the mixture was allowed to stand at 50 ° C. for 12 hours.
After standing, the soft vinyl chloride sheet containing a plasticizer was visually observed and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 1.
(Evaluation criteria)
A: There was no transfer of dye to the soft vinyl chloride sheet containing plasticizer, and high plasticizer resistance was confirmed.
B: The transfer of the dye to the soft vinyl chloride sheet containing a plasticizer was confirmed to some extent, but there was no problem in practical use.
C: Many dye transfers to the soft vinyl chloride sheet containing a plasticizer were confirmed.

<< Measurement of protruding area ratio of antibacterial particles >>
The printed matter produced in the above antibacterial property evaluation was prepared, and the peeled layer contained in the printed matter was observed and observed using a non-contact surface measuring device VertScan (manufactured by Ryoka System Co., Ltd.) using an optical interference method. The ratio of the surface area of the exposed antibacterial particles to the area (protruding area ratio) was calculated. The calculation results are summarized in Table 1.

10: Thermal transfer sheet, 11: First substrate, 12: Release layer, 13: Transfer layer, 14: Adhesive layer, 15: Colored layer, 16: Back layer, 20: Intermediate transfer medium, 21: Second substrate, 22: Release layer, 23: Receptive layer, 30, 40: Printed matter, 31: Transferee, 32: Transferee substrate, 33: Receptor layer, 41: Transferee substrate (transferred body)

Claims (13)

A first substrate and a transfer layer having at least a release layer are provided.
The release layer contains a resin material and antibacterial particles.
The average particle size of the antibacterial particles is 1 μm or more and 8 μm or less.
A thermal transfer sheet in which the content of antibacterial particles with respect to 100 parts by mass of the resin material in the release layer is 2.8 parts by mass or more and 8 parts by mass or less. The thermal transfer sheet according to claim 1, wherein the thickness of the release layer is 0.5 μm or more and 3 μm or less. The thermal transfer sheet according to claim 1 or 2, wherein the ratio of the average particle size of the antibacterial particles to the thickness of the release layer (average particle size of antibacterial particles / thickness of the release layer) is 1 or more and 8 or less. .. The thermal transfer sheet according to any one of claims 1 to 3, wherein the antibacterial particles are phosphates carrying antibacterial metal ions. The thermal transfer sheet according to any one of claims 1 to 4, wherein the release layer contains an antistatic material. A printed matter produced by using the thermal transfer sheet according to any one of claims 1 to 5.
Transferred body and
A printed matter including the transfer layer. The method for manufacturing a printed matter according to claim 6.
The step of preparing the thermal transfer sheet and the transferred body according to any one of claims 1 to 5.
A step of transferring the transfer layer included in the thermal transfer sheet onto the transfer target, and a step of transferring the transfer layer.
A method for manufacturing a printed matter, including. The method for producing a printed matter according to claim 7, further comprising a step of irradiating the transferred body with a sterilizing line after the transfer of the transfer layer. A second base material, a release layer, and a receiving layer are provided.
The release layer contains a resin material and antibacterial particles.
The average particle size of the antibacterial particles is 1 μm or more and 8 μm or less.
An intermediate transfer medium in which the content of antibacterial particles with respect to 100 parts by mass of the resin material in the release layer is 2.8 parts by mass or more and 8 parts by mass or less. A printed matter produced by using the intermediate transfer medium according to claim 9.
Transferred body and
With the peeling layer
A printed matter comprising the receiving layer. The method for manufacturing a printed matter according to claim 10.
The step of preparing the intermediate transfer medium and the transferred body according to claim 9, and
A step of forming an image on the receiving layer included in the intermediate transfer medium, and
A step of transferring the release layer and the receiving layer included in the intermediate transfer medium onto the transferee,
A method for manufacturing a printed matter, including. The method for producing a printed matter according to claim 11, further comprising a step of irradiating the transferred body with a sterilizing line after the transfer of the peeling layer and the receiving layer. A stamp manufacturing system for manufacturing the stamp according to claim 6 or 10.
With a thermal transfer printer
Sterilization mechanism and
A print manufacturing system equipped with.

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